JP6830172B1 - A photocurable antifogging resin composition and a laminate having a cured layer thereof. - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photocurable resin composition having excellent antifogging property due to a low water contact angle and having strong antiviral and antibacterial properties, and a laminate having a cured layer thereof. A monovalent copper compound containing an acrylic binder, a monovalent copper compound, and a photopolymerization initiator is blended in an amount of 0.01 to 9.0 parts by weight with respect to 100 parts by weight of the acrylic binder. This is a photocurable antifogging resin composition having antiviral and antibacterial properties, characterized in that the water contact angle of the cured film is 10 ° or less. [Selection diagram] None

Description

The present invention relates to an antiviral / antibacterial antifogging resin composition having a low water contact angle, which is cured by irradiation with light such as ultraviolet rays, and a laminate having a cured layer thereof.

As the epidemic of infectious diseases typified by COVID-19 spreads, the risk of infection by medical personnel such as doctors and nurses is increasing. In order to protect yourself from such infections, it is necessary to protect the eyes, nasal cavity, and oral mucosa from exposure to pathogens contained in saliva droplets of infected people, and goggles, protective glasses, face shields, etc. are used as protective tools. It is used.

Of these, the face shield is an effective tool that can protect the infection through the mucous membrane in a wide range in places where there is a high risk of direct contact with the infected person, but since it has a structure that easily retains heat, wear glasses in particular. When used, there was a problem that fogging was likely to occur. When reusing a face shield that has been used once, it is necessary to thoroughly and surely clean and disinfect the inside and outside of the shield in order to prevent reinfection caused by the attached virus.

As a coating composition that can be used for such a face shield and can reduce the occurrence of fogging, for example, a composition containing a porous inorganic oxide and a surfactant containing a hydrophilic anionic group has been proposed (Patent Document 1). ). However, since this composition does not have antiviral properties, the risk of reinfection due to the attached virus could not be sufficiently reduced, especially when the face shield is reused. Therefore, there has been an increasing need for a coating agent that can be easily applied to a plastic base material, has antifogging properties, and can kill viruses.

Japanese Unexamined Patent Publication No. 2010-202881

An object of the present invention is to provide a photocurable resin composition having a low water contact angle, which is excellent in antifogging property, and having strong antiviral and antibacterial properties, and a laminate having a cured layer thereof.

The invention according to claim 1 includes an acrylic binder (A), a monovalent copper compound (B), and a photopolymerization initiator (C) in order to solve the above-mentioned problems. (A) A photocurable anti-virus and antibacterial property characterized in that the blending amount with respect to 100 parts by weight is 0.01 to 9.0 parts by weight and the water contact angle of the cured film is 10 ° or less. A frost resin composition is provided.

The invention according to claim 2 is characterized in that the water contact angle of the film obtained by curing the simple substance (A) with a polymerization initiator is 10 ° or less after being immersed in boiling water for 1 hour. Provided is a photocurable antifogging resin composition having the above-mentioned antiviral and antibacterial properties.

The antiviral / antibacterial property according to claim 1, wherein the water contact angle of the cured film is 15 ° or less after being immersed in boiling water for 1 hour. Provided is a photocurable antifogging resin composition having the above.

The invention according to claim 4 provides a laminate having a cured layer of a photocurable antifogging resin composition having antiviral / antibacterial properties according to any one of claims 1 to 3 on a base material.

Since the photocurable resin composition of the present invention has excellent antifogging properties and strong antiviral / antibacterial properties, it is useful as a coating agent to be applied to films, sheets, and laminates used in medical applications such as face shields. ..

Hereinafter, the present invention will be described in detail.

The composition of the composition of the present invention is a binder (A), a monovalent copper compound (B), and a photopolymerization initiator (C). In addition, in this specification, (meth) acrylate includes both acrylate and methacrylate.

The acrylic binder (A) used in the present invention is a hydrophilic photocurable resin that disperses (B). In the present invention, the water contact angle performance of the present invention may be exhibited by a single material as a binder for forming an antiviral layer, but a material combined with another material is also regarded as a binder in the present invention. Examples of the material to be composited include materials other than (B), such as a surfactant and a compound having a siloxane bond.

The (A) has a water contact angle such that the cured layer of the composition containing (B) has a water contact angle of 10 ° or less, but the water contact angle is preferably 8 ° or less, and more preferably 6 ° or less. preferable. In order to obtain stable antifogging and antiviral properties, it is preferable that the water contact angle is stable and low even under harsh conditions. Specifically, it is preferable that the water contact angle of the simple substance (A) without (B) is 10 ° or less even after being immersed in boiling water for 1 hour. Further, the water contact angle of the cured film containing (B) is preferably 15 ° or less even after being immersed in boiling water for 1 hour. In the present specification, the water contact angle is a value measured based on the intravenous drop method of JIS R 3257: 1999.

In order to make the water contact angle of the film obtained by curing the simple substance (A) with a polymerization initiator 10 ° or less even after being immersed in boiling water for 1 hour, simply select a binder containing a hydrophilic group. Is not sufficient. For example, the membrane structure should be such that specific anionic hydrophilic groups are inclined (segregated) from the inside of the membrane to the surface of the membrane, and the anionic hydrophilic groups are concentrated near the surface and exist at a high concentration. Is preferable. Specific examples of formulations that realize such a film structure include a composition containing sulfopropyl potassium acrylate, sodium distearyl sulfosuccinate, and polyfunctional (meth) acrylate, and sulfopropyl potassium acrylate and sodium dihexyl sulfosuccinate. Examples thereof include a composition containing a polyfunctional (meth) acrylate, and as the polyfunctional (meth) acrylate, an EO-modified bisphenol A diacrylate or the like can be used. Examples of commercially available binders having a water contact angle of 10 ° or less even after being immersed in boiling water for 1 hour include Z-948L (PGM) (trade name: manufactured by Aica Kogyo Co., Ltd., acrylate-based).

The monovalent copper compound (B) used in the present invention plays a role as an antiviral agent / antibacterial agent. Generally, metal-based materials having antiviral properties include compounds containing copper, silver, titanium, tin, iron, nickel, zinc and the like, but among these, monovalent copper does not require the addition of a stabilizer. Therefore, it is characterized by a high degree of freedom in designing constituents and high antiviral and antibacterial properties. Examples of the monovalent copper compound having antiviral and antibacterial properties include chlorides, iodides, bromides, oxides, thiocyanates and the like.

The mechanism of the antiviral / antibacterial agent of (B) is that when a monovalent copper compound comes into contact with a virus or a bacterium, a monovalent copper ion is generated, and the monovalent copper ion reacts with oxygen. It is thought that the principle is that active oxygen is generated and the active oxygen and copper ions kill viruses and bacteria. The applicant disperses this monovalent copper compound in a highly hydrophilic binder and mixes it. It has been found that the antiviral / antibacterial properties can be made more stable and excellent by setting the amount in a specific range. The reason is not always clear, but since it is a highly hydrophilic film, moisture in the air is easily adsorbed, and monovalent copper ions generated when a monovalent copper compound comes into contact with a virus or bacteria are generated. It is thought that it forms an environment that is more likely to occur.

The blending amount of the above (B) with respect to 100 parts by weight of (A) is 0.01 to 9.0 parts by weight, preferably 0.02 to 9.0 parts by weight, and further 0.03 to 8.5 parts by weight. preferable. Sufficient antiviral and antibacterial properties can be ensured when the content is 0.01 parts by weight or more, and sufficient steel wool resistance can be ensured when the content is 9.0 parts by weight or less.

The photopolymerization initiator (C) used in the present invention generates radicals by irradiation with ultraviolet rays, electron beams, etc., and the radicals trigger a polymerization reaction, and is benzylketal-based, acetophenone-based, or phosphine oxide-based. A general-purpose photopolymerization initiator can be used. By arbitrarily selecting the light absorption wavelength of the polymerization initiator, curability can be imparted over a wide wavelength range from the ultraviolet region to the visible light region. Specifically, 2.2-dimethoxy-1.2-diphenylethane-1-one as a benzyl ketal system, 1-hydroxy-cyclohexyl-phenyl-ketone and 1- [4- (2- (2- (2-)) as an α-hydroxyacetophenone system. Hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1-one is a 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1 as an α-aminoacetophenone system. -On includes 2.4.6-trimethylbenzoyl-diphenyl-phosphine oxide and bis (2.4.6-trimethylbenzoyl) -phenylphosphine oxide as acylphosphine oxide systems, alone or in combination of two or more. Can be used in combination.

Among these, it is preferable to contain an α-hydroxyacetophenone system that does not easily yellow, and examples of commercially available products include Omnirad 127, Omnirad 184, and Omnirad 2959 (trade name: manufactured by IGM Resins). Among these, Omnirad 2959, which has less yellowing and excellent scratch resistance, is particularly preferable. The composition of the above (C) with respect to 100 parts by weight of the component (A) is preferably 2 to 10 parts by weight, more preferably 3 to 8 parts by weight.

The resin composition of the present invention contains anti-pigment agents, antioxidants, ultraviolet absorbers, sensitizers, flame retardants, fillers, organic fine particles, inorganic fine particles, dispersants, silanes, as required, as long as the performance is not impaired. Additives such as coupling agents, leveling agents, defoamers, antistatic agents, polymerization inhibitors, colorants such as pigments, dyes and pigments, and plasticizers can be used in combination.

When the resin composition of the present invention is applied to a plastic substrate, toluene, isobutanol, ethyl acetate, butyl acetate, hexane, cyclohexane, cyclohexanone, methylcyclohexanone, acetone, methyl ethyl ketone, etc. are used to improve the coating characteristics. It may be diluted with a solvent such as methyl isobutyl ketone or propylene glycol monomethyl ether (hereinafter referred to as PGM). An example of the solid content when diluting is 20 to 50%, but there is no particular specification, and the viscosity can be appropriately set so as to have a viscosity that is easy to apply.

The base film to which the resin composition of the present invention is applied includes a polyester film, a triacetyl cellulose film, a polycarbonate (hereinafter referred to as PC) film, a polysulphon film, a nylon film, a cycloolefin film, and an acrylic (hereinafter referred to as PMMA) film. , Polygonic film, ABS film, polyolefin film, PVC film, PVA film and the like. Among these, polyester film and acrylic film are preferably used from the viewpoint of transparency, moldability and the like. The thickness of the film may be approximately 25 μm to 500 μm.

For the purpose of improving the adhesion, the base film to which the resin composition of the present invention is applied is subjected to surface unevenness treatment by primer treatment, corona treatment, sandblasting method, solvent treatment, etc., chromic acid treatment, ozone. Surface treatment such as surface oxidation treatment such as ultraviolet irradiation treatment can be performed.

Examples of the method for applying the resin composition of the present invention to the base film include a bar coater method, an applicator method, a curtain coater method, a roll coater method, a gravure coater method, a reverse coater method, a comma coater method, a lip coater method, and a die coater method. A known method such as a method can be applied. As the coating film thickness, a dry film thickness of 1 to 20 μm is generally exemplified, but it is not particularly specified and can be selected at any time.

After applying the resin composition of the present invention, it is dried at 60 to 120 ° C. to volatilize the solvent and then cured using an ultraviolet irradiator. As a light source, a known light source such as a high-pressure mercury lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, a xenon lamp, an LED lamp, or an electrodeless ultraviolet lamp can be applied, and the ultraviolet irradiation condition is 500 mW / cm ^2. in the irradiation intensity of ^{~3,000mW / cm 2, 100mJ / cm} 2 ~2,000mJ / cm 2 can be exemplified as the cumulative amount of light.

Viruses are roughly classified into a type that is wrapped in a membrane called an envelope containing lipids and a type that does not have an envelope. The type with envelope is mostly composed of lipids and can be easily destroyed with a disinfectant such as ethanol or soap, whereas the type without envelope is generally highly resistant to disinfectants. It is said. The resin composition of the present invention has very good antiviral properties against both of them.

The resin composition of the present invention is particularly suitable for use in medical applications. For example, in addition to protective tools such as goggles, protective glasses, face shields, eye shields, and mouse shields, plastic films, plastic sheets, plastic plates, etc. provided between infected persons and medical personnel and between infected persons and infected persons. By applying it to partitions, stakes, etc., reinfection due to the attached virus can be prevented.

Hereinafter, the present invention will be described in detail based on Examples and Comparative Examples, but specific examples are shown and the present invention is not particularly limited thereto. Unless otherwise specified, the measurement was performed under the conditions of room temperature of 25 ° C. and relative humidity of 65%. The blending amount indicates the part by weight.

Example As the above (A), Aitron Z-948L (PGM) (trade name: manufactured by Aica Kogyo Co., Ltd., acrylate-based, solid content 40% by weight, see below for wet characteristics *) is used as the above (B). A monovalent copper compound is blended as (C) above with Omnirad 2959 (trade name: manufactured by IGM Resins) so that the ratio in solid content is as shown in Table 1, and the solid content is further increased to 40%. The coating composition of Examples was prepared by diluting with PGM and stirring until uniformly dissolved and dispersed.
* Itron Z-948L: With a formulation in which a monovalent copper compound is removed from Example 1, the water contact angle of the film coated on a PET film so that the film thickness after drying is 2 μm and photocured is , Less than 10 ° even after soaking in boiling water for 1 hour.

In addition to the materials used in the examples, RUA076MG (trade name: manufactured by Asia Industries, Ltd., hexafunctional urethane acrylate) and DPHA (dipentaerythritol hexaacrylate) were used as binders to prepare the coating agent composition of the comparative example.

Table 1

Adjustment of evaluation film Using the compositions of Examples and Comparative Examples prepared above, U403 (trade name: polyester film manufactured by Toray Industries, Inc., thickness 100 μm) was adjusted to have a dry film thickness of 2 μm. The film was coated, dried in a constant temperature bath at 80 ° C. for 1 minute, and then irradiated with ultraviolet rays with a high-pressure mercury lamp so that the output was 1300 mW / cm2 and the integrated light amount was 100 mJ to prepare an evaluation film.

The evaluation method was as follows.

Antiviral activity value: Measured by the plaque measurement method of ISO 21702: 2019. Influenza A virus and feline calicivirus were used as test viruses, and the virus infectivity titer was measured after 24 hours. The difference in virus infectious titer from the blank film was defined as the antiviral activity value, with a value of 2.0 or more as ◯ and a value of 2.0 or less as x.

Water contact angle: According to the static drip method of JIS R 3257: 1999, using DMs-400 manufactured by Kyowa Interface Science Co., Ltd., using a sample in a normal state and after boiling for 1 hour, water was dropped at room temperature and allowed to stand for 30 seconds. The contact angle was measured, and in the normal state, less than 10 ° was evaluated as ◯, 10 ° or more was evaluated as x, and after 1 hour of boiling, less than 15 ° was evaluated as 〇, and 15 ° or more was evaluated as x.

Steel wool resistance: A load of 200 g / cm2 was placed on steel wool # 0000 and reciprocated 10 times. Those that were not scratched by visual observation were marked with ◯, and those with scratches were marked with x.

Evaluation result <br /> Table 2

Each composition of the example obtained good results in all evaluations of antiviral activity value, water contact angle, and steel wool resistance.

On the other hand, Comparative Example 1 in which the amount of (B) is large is inferior in steel wool resistance, Comparative Example 2 not containing (B), and Comparative Examples 3 and 4 having a large water contact angle of the cured film show antiviral properties. None of them were suitable for the present invention.

Claims (4)

It contains an acrylic binder (A), a monovalent copper compound (B), and a photopolymerization initiator (C), and the blending amount of the (B) with respect to 100 parts by weight of the (A) is 0.01 to. A photocurable antifogging resin composition having an antiviral and antibacterial property, which is 9.0 parts by weight and has a water contact angle of 10 ° or less. The antiviral / antibacterial property according to claim 1, wherein the water contact angle of the film obtained by curing the simple substance (A) with a polymerization initiator is 10 ° or less after being immersed in boiling water for 1 hour. A photocurable antifogging resin composition having. The photocurable antifogging resin having antiviral and antibacterial properties according to claim 1 or 2, wherein the water contact angle of the cured film is 15 ° or less after being immersed in boiling water for 1 hour. Composition. A laminate having a cured layer of a photocurable antifogging resin composition having antiviral / antibacterial properties according to any one of claims 1 to 3 on a base material.